Subresinous acylated polyamine



Patented Dec. 12, 1944 SUBRESINQUS ACYLATED. POLYAllCINE Melvin De Groote, University City, and" Bernhard 'Keiser, Webster'Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No-Drawing. Original application June 27, 1940, SerialNo. 342,724. Divided and this application"ctober4,'1941, Serial No. 413,697

:9. Claims. (o1. 26c f404-.5)

I This applicationis a division ofcurpending applicationiSerial-No. 342,724, filed June 27, 1949, which subsequently. matured ,as .U. S. P. 2,262,358, dated November 11,1941.

The object of .ourinvention isto provide a new material or composition of matter, that isparticularly adapted for use as ,a demulsifier in the resoluticno'f crude oil emulsions. "Forinstance, the said new material .or composition of matter may be used as a break inducerin doctor treatmento'f the 'kind'intended to sweeten gasoline.

subterranean strata, reference vis made to (the procedure described in detail in U. S. .Patent' No.

2,233,382, dated February 25, 1941,. to ,Melvin'De Groote and Bern-hard Keiser. As. tousing compounds-of the kind herein described "as surface tension depressants or demulsifiers, in combination withmineral acid for acidizati'on of oilbearing strata, reference is made to U. S. Patent 'No. 2,233,383, dated February "25, 1941 to Melvin De Groote and'BernhardjKeiser.

The new composition of matter'which' constitutes our present invention canbe produced by re-acting a polybasic carboxy .acidcompound containing .at least one high molecular weight carboxy acid radical, with a polyamine of the following types:

in which a: is a small whole number lesszthan .10 but including .zero, T represents any suitable oxygenated divalent linking radical of the ;type tcbe subsequently.describedyand D maybe'hydrogen, .alkyl, .alkylol, hydroxyalkyloxyalkyl,

. aminoalkyl, RCO, RCOiOX, and RCQQ'X', in

which RC0 is an acyl radical derived -:from .a lowermolecular weight carboxy acid having six carbon atoms or less; RCOQX is a-radical .in which OX represents a divalent radical obtained at least hypothetically by the-removal of a hybined with a hydroxylated alkylene diamine of.

. acylation product, i. e., a product which involves droxyl hydrogen atom; from an alkylol radical; and RCO'OX' denotes a radical 1 in 'which OX represents a radical "derived or obtained at least hypothetically by the 'removal o'f-a hydroxyl hy- -drogen atom from a hy'droxyallq loxyalkyl radical. Incidentally, as 'willbe subse'quentlyiexplaine'd, D may represent certain other'substituents which will be 'describedhereafter. Said new material or composition of matter. has unusual effectiveness-asa demuls'ifier for resolving petroleum emulsions ofthe'water in-oil type.

Such high molecular, weight carboxy acid can be united with apolybasicacid in two general ways: The high molecular weight carboxytacid, usually a monocarboxy *a'cidpi'may z'containzaan I alcoholic hydroxyl group as part. of the acyl radical. For instance, ricinoleic acid,- hydroxystearic acid, and the like, serve to.illustrateithis particular type. In other instances, theihigh molar carboxy acid may be combined with a polyhydric alcohol in such a way that there is available' at leastone hydroxyl attached =to.the polyhydric alcohol residue, which may be esterified with or united to the polybas'ic carboxy acid.- jlVion'ostearin, mononaphthenin, ethylene glycol monostearate, and thellike, illustrate this type. Monoricinolein illustrates a type which includes both varieties of hydroxyl radicals. r

In a general way, the'most feasible procedure for the manufacture or the "compounds of it'he kind herein contemplated is to combine a polybasic carboxy acid, and particularly, a dibasic acid, such as ;phthalic acid oranhydride with the selected hydroxylated high molecular weight carboxyacid body, in such a-manner as. to *obtaina..material which has at least one lfree 'oarboxyl radical-in other words, ,inaessen'ce, ':a fractional ester. Such fractional ester can then be com-'- the kind hereinafter described to produce an either ester linkages or amide linkages, or both. The expression fractional ester is employed in i the hereto appended claims .to indicate a compound containing at least one free carboxyl radical, attached to a polybasic acid nucleus, and which may or may not contain one or more hydroxyl radicals.

The expression higher molecular weight carboxy acids is an expression frequently employed to refer to 'certain organic acids, particularly monocarboxy acids, having more than 6 carbon atoms and generally less than {10 carbon; atoms. The commonest examples includethe deter-gent forming acids, i. .e., thoseiacids which combine i with alkalies to produce soap or soap-like bodies.

As to a complete list of suitable high molal acids, reference is made to our aforementioned U. S. Patent No. 2,262,358, page 1, right hand column, line 36, through page 2, left hand column, line 54. It is noted that emphasis is placed on the higher fatty acids, particularly the unsaturated higher fatty acids having 18 canbon atoms, and On the mixturesof higher fattyacids as they appear in naturally-occurring glycerides.

Alkylene polyamines, characterized by the fact that two or more amino nitrogen atoms are joined'by an alkylene radical, are well known. Such compounds may be either open chain compounds of the following general formulas:

where a: is a whole number; or they may be ring 1 compounds having the general formula:

o2H..NH)..c,H..NH-

where a: is a whole number. exemplified by 'diethylene triamine,

(NH2.C2H4.NH.C2H4.NH2)

triethylene tetramine,

f (NH2.C2H4.NH.C2H4.NH.C2H 4.NHz)

and tetraethylene pentamine,

(NHz.C2H4.NI-I.C2H4.NH.C2H4.NH.C2H4.NH2)

Examples of the second group are diethylene diamine.

and triethylene triamine:

. I NHC ILNH In the above formulas the radical CzI-Li'is simply a divalent linking radical. Thus, preceding formulas may be rewritten as follows: Y

T 'r i 'r NH.T.NH in which T represents any suitable divalent linkingradical. If T is 'an oxygenated divalent linking radical of the kind'to be described, and if The first group is such polyamines are acylated so as to introduce an acyl radical from a higher molecular weight carboxy acid of the kind previously defined, one

obtains a new composition of matter and a com pound or a variety of compounds which are particularly effective asdemulsifiers for water-inoil emulsions.

Generally speaking, the oxygenated divalent linking radical is exemplified by three types: the keto type, in which the conventional car bonyl linkage appears; the ether type, in which the conventional ether linkage appears; and the hydroxylated type, in which the conventional alcoholic hydroxyl radical appears. One of the best known examples are compounds obtained from fic' dichloralkyl ethers, instead of alkylene dichlorides. Such compounds are characterized by the preceding formulas if one adds the proviso that in such formulas T shall represent the divalent radical CHzCI-IzOCI-IzCHz. As to the manufacture of such compounds, seeU. S. Patent No. 1,919,301, dated July 25, 1933, to Morton.

one may use the propyl ether halogen derivative or other suitable compound. If derived from ammonia, such diamines may be alkylated in the manner commonly employed for alkylating ordinary amines, i. e., monoamines. Alkylation may result in products which are symmetrically or non-symmetrically alkylated; The symmetrically alkylated diamines are most readily obtainable. For instance, alkylated products may be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetylchloride, andthe like. Such reaction products result in the formation of hydrochloric acid, and the resultant product consists of an amine hydrochloride. The conventional method forconversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group; but, as a matter of fact, a radical may be introduced characterized by the fact that the carbon atom chain is interrupted at least once by an oxygen atom. In other words, alkylation may be accomplished by compounds which are essentially alkyloxyalkyl chlorides, as, for example, the following:

As a matter of common knowledge, reactions involving ammonia and an alkyl ether dichloride probably go through an intermediate stage which involve the formation of amino-alkyl ether halide. As a result, one has another suitable procedure for manufacture of the diamines, i. e.,

etc. Various other procedures may be employed for comparable secondary amines, in whicln'vario'us alkyl' radicals- {previously mentioned appear twice and are types in: which two :dissi'rnilarraidis cals appear; for instance,-amyl butylamine; hexyl octyl'amine, etc; Furthermore, compounds: may be derived, by reactions involving alkylene dichlorides and a-rmi'xtu're o'f ammonia-and amines, or a mixture of two diiferent'vamines'.

It is-known that there are numerous-other com-- pounds which are akinto the dichloralliyl'ethers, in that they are labile or'reactive alpha-omegadichloro' derivatives; 3 Thus, well known reactants which supply-a divalent linking radical I of the kind indicated by T in' previous formulas ihcl'udezdiohlorodiethyl ether (ClCzHiOGHiCU-g chloroethoxy' triglycol dichloride; tetraglycol' iiicliloride; dichlorodiisopropyl ether ClCsI-Iw OCzHqCl) dichlorodiisobutyl ether- (ClCiHgOCiHCD glyc erol dichlorhydrin; methyl glycerol dichlorl'iydrin; polyglycerol dichl'orhydrins; dichloracetone derived from acetone; dichlormethylpropyl ketone CHzCl c Hs-C OCH\ producing polyamines: of the kind described. For instance, reference ismade to our co-pendingtap plicationfor-patent Serial No. 273,278, filedMay 12, 1939, which subsequently; matured asU. S; Pat:- ent No. 2,293,494, dated-August 18, 1942; In'said application there is described the conversion of triethanolamine intoan alcoholate, such as monoalcoholate, by means of caustic soda and the like,

and subsequently uniting two moles of such com-' pound-by means of a material such asglycerol dichlorhydrin. Similarly, thedialooholate might be treated in the same manner; Incidentally,

' suchalcoholatesmay be derived-from'hydroxy alkyl ethers of tertiaryamines, as w'ellas: materials of the kind exemplified by triethanolamine. See U. S. Patent No; 13923178, toi Ulrich,

, Nuesslein', and Koerding, dated August 22, 1933.

Other suitable procedure ,involvesf'hydroxya rine atoms,'one is aptto obtain varying amounts of such higher polyamines. For the sake of brevity, further indications will be limited to. pro,- cedures" for. making various suitable .polyamines.

Suchsuitable polyamines'will be the following:

I Among produets commerciallyavailable is ;--1,3'

diamino-2- propanol'; which is an: especially suit able reactant: r

It has been-pointed out that polyaminesmf the kind previously described may" be produced or reacted in" such a manner that the amino hydrogen atom is i replaced byan 1 'alkyl" radical, a hydroxyalk'yl radical; a hydroxyalkyljoxyalkyl radical; ortl'ie'like; It iswellk nown that-certain' other modifications can be'obtair'ied' by conventional procedures For instance, one may introd'uce acyl l radicals" derived" from acids 1 having 6" carbon atoms or less;- such as acetic acid, butyric* acid," and theqlike: Such products are obtained by treatment with acetic anhydride, acetyl chloride; or equivalentreactants; Fur thermore, it is'lfnown that one can obtain derivatives of amines of the kind" described by" reactions' wi'th chlorl'iydrins---derived from polyglycols, polyglycerols and i the: like; such as diglycerol chlorhydrin', the chlorhydriii'derived from the diliydrici-alcohob obtaineu' by 'etherizing two moles 1 of dietliyleneg-lycoli etc. Similarly,- a'rnir'ro h' drogens maybe-substituted by 'reaction with com pounds I of the kind typified by ethyl chlorace ta-te; i] e:-, esters of"carhoxynci'dsiin which' an. aIph'a liydrOgen has been "substituted by; chlorine.

Similarly; as *h'as-beensuggested previously, amino Certain other compounds: may be ,1ooked" .up'on C as instances in which one'ot'the' aminoliydrogen' atoms of a polyamine, particularly a diamine, has been replaced by an amino alkyl group. For

. the sake of brevity, in the hereto appended claims the expression "alkyloxyalky 'is intended to include thetype of oxyhydrocarbon radical where th hydrocarbon chain is interrupted mor than once by an oxygen atom. Similarly, since materials such as ethyl chloracetate are sometimes spoken of as alkylating agents, it is intended that the expression alkyl will include the type of radical so introduced, i. e., a radical exemplified by the following: i r

CHzCOOCzHs although, strictly speaking, it is not, of course,

an alkyl radical.

Summarizing what has been said thus far, it is apparent that one could readily obtain amines oi the following type:

in which :n isa small whole number less than 10 but including zero, T has its previous significance and Dmay be hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, RCO, RCODX, and RCODX, in which RC is an acyl radical derived from a lower molecular weight carboxy acid having 6gcarbon atoms or less; RC0.0X is a radical in which OX represents a divalent radical obtained at least hypothetically by the removal of a hydroxyl-hydrogen atom from an alkylol radical; and RC0.0X denotes a radical in'which OX represents'a radical derived, at least hypothetically, by the removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical. If one adds the proviso that there must be a reactive hydrogen atom present in such polyamine, i. e., a hydrogen atom linked to a nitrogen atom or to an oxygen atom, one then has an acylation-reactive polyamine.-

In other words, such polyamine can be acylat ed so as to introduce a polybasic carboxy acid acyl group in the same manner that any other amine can be acylated, i. e., an ordinary mono amine or diamine. Thus, the methods for acylating ordinary monoamines which are primary or secondary are well known. Likewise, suitable procedure for acylating diamines, including hydroxylated diamines, is well known. In the present instance, as a variation, one employs a suitable polybasic acid or any functional equivalent. For convenience, amines of the above type which can be acylated, i. e., have present a reactive hydrogen atom, will be referred to as acylation-reactiv amines. Such acylation products may be of the amide type, in other words, of a type in which the acyl group is directly attached to the amino nitrogen atom; or they may be of the ester type, where the acyl group replaces a hydroxylhydrogen atom, and thus is linked to a nitrogen atom through a carbon chain; or the r Ins understood that thenew composition of matter herein contemplated,and particularly,.for v use as a demulsifier', may be prepared in any suitable manner. As has beenstated, it is our preference to obtain an acylation-reactive amine of the type or kind just described, and react the same with a polybasic carboxy acid compound or its functional equivalent. It is our preference to use the type of polybasic aci-d compound which is characterized ;by the-presence of an'acyl radical of the detergent-forming acid type, which includes fatty acids, resin acids, and petroleum acids. Such petroleum acids may. be naturallyoccurring acids,such as naphthenic acid, or may be obtained by; the oxidation of paraifin or the like. Of the various detergent-forming acids which may be'employed to supply the detergent acid type acyl radical, we prefer to use fatty acids, and most particularly, hydroxylated fatty acids,such as ricinoleic acid. Previous reference has been made to the introduction of an amin'oalkyl radical in place of an amino hydrogen atom. The availability of a compound of the followingtypes:

v .C 2H4OH CICZHIQN C2H4OH CICzHlN V would permit the introduction of a hydroxyalkylamino radical. However, the introduction of such type radical is more feasibleb-y introducing an aminoalkyl radical from a compound such as, for instance, chloramylamine The. use of such halide permits the introduction of the aminoalkyl radical NH2;C5H1o. Such radical, after being-introduced into the polyamine nucleus, whether prior to or after acylation, can, of course, be treated with an oxyalkylating agent, such as ethylene oxide, or any similar a 5 alkylene oxide' or with glycid, epichlorhydrin and. other reagents, so as to convert one or both of the amino hydrogen atoms in the above described aminoalkyl radical, into ahydroxyalkyl radical, or; in the case of ethylene oxide, into a C2l-I4OH radical. Needless to say, such a radical, which is, i

in which a: is a small whole number including ,0, but in any event, less than 10, and preferably 1 to 4; T is an oxyhydrocarbon' radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, R C O, R, C O O X, RCOOX', RCOOX", RCOOX; RC0 is an acyl radical derived from a lower molecular weight carboxy acid having 6 carbon atoms or less;

line-.39; through page 6, right hand column liner represents a divalent radical obtained at least hypothetically by removal of a hydroxyl hydro-, gen atom from an alkylol radical; OX representsa radical derived at least hypothetically by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived a least hypothetically" by the removal of an amino hydrogen atom from an aminoalkyl radical; .and O' X" represents a radical derived at least hypothetically by removal of a hydrogen atom from a hydroxyalkylamino radical.

Attention is directed to the fact that the word amidification has been applied to the reaction involving the replacement. ofan amino hydrogen atom by an acyl radical,withoutconventional limitation to a reaction involving ammonia. The replacement of the amino hydrogen atom of a primary amine or a secondary ar'ni'ne'- by an acyl radical has been considered as being amidification, rather than the formation of a substituted amide, or the formation of an imide or substituted imide. Such obvious departure from conventional nomenclatures has been for purposes of simplicity and to show the similarity between certain reactions.

It is to be understood that the compound herein contemplated may be manufactured in any suitable manner;' and onei's not dependentupon following the exact procedure previously outacids themselves, one may use any suitable functional equivalent, and particularly, the anhydrides. We prefer to use oxalic-acid, maleicacim.

and phthalic-acid. In the-use ofmaleic acid and phthalic acid, we particularly prefer to use the anhydride, i. e., maleic' ahhydride andphthalic anhydride. It is-understood that in the hereto attached claims any references to the acid or the anhydride is intended to be interchangeable;

The manufacture of fractional esters; charac terized by having'present: (a) a detergent' fo'r'm ing acid radical; and (b)' a free carboxyl radical directly attached to a polyb-asic acid residue, is

well known. Such materialshavefonnd. utility in various arts. The same procedure which is employed in connection with the detergent-forming acids would apply to any ofthe high molecular" weight carboxy acids previously described; and particularly, those which are primarily mono carboxy in nature.

Likewise, the procedure followed in respect to the detergent-forming acids is best exemplified by the fatty acids-although obviously, the same procedure is' equally suitable for resin acids and petroleum acids, whether naturally-occurring or" obtained by the oxidation of paraflin or the like.

In order to eliminate lengthy detailed description of these particular materials, which are Well known compositions of matter, reference is made" to U. S. Patent No. 2,166,431, date'dJiily 18, 1939; to Melvin De Groote, and particularly, to the subject-matter which appears on page4, right hand column, line 36, through page 5, right hand column', line 16; and also to U1 s; Patent N01 2,166,433, dated July 18, 1939, to Melvin" De Groote, beginning on page 4, right hand column;

. acids themselves;

In subsequentexamples reference will be made to the manufacture of our. new composition of matter by reacting a pol-ybasic'acid derivative ofl a detergent-forming acid compound, or, for that 1 diamineofthe kind previously described. It is understood, however, that the compositiongofmatter could beobtained inany suitable manner,

and that-in the hereto attached claims it is not intended that there shall be any limitation as to th procedure employed: For instance, one might first combine, the selected amine withapolyibasic carboxy acid by means of anacylation reaction in such a manner as to have present a freecarboxylradical attached to thepolybasic carboxy acid. Suchproduct then mightbe esterified witha hydroxylated detergent-forming acid bodyor the like, for instance, triricinolein, to give a compound ofthe kindherein contemplated. Wefind, however,-that the most feasible procedure isto" employ the method previously suggested, although,as-has beenremarked, itis not intended in any manner to be a limitationin regard to thenature of the composition; of matter herein contemplated.

It is; understood that the compounds the 1 kind herein contemplated may contain acylrad icals derived from polybasic carboxy acids andnot united to the amine residue.

selected amine in such-a manner that only one phthalic acid radical is united with the amine.

The other phthalic acid radical may remain-in the acidic state, or the carboxy hydrogen atom could be replaced inany'suitablemannenas described. Furthermoradf a tribasic acid is em;-

ployed such-as citric acid,thentwo carboxy radicals might beemployed to unitethe carboxy detergent-for-ming residue or the: like with the i amine residue, and the remaining car-boxy radical could remain assuch, i. e., in the acid stat ',01 again, it might be so treated'that the acidic hydrogen atom is replaced in the manner sub- 'sequently described. Q

Thus, in the manufacture or'var-ious conipbsil tions. of matter of the kind herein contemplated; it is to be understoodthat" any residual carto ylic hydrogen atoms de'rivedfrom p'olybasiccar boxy acids may remain as such, or maybe-re-v placed by any Suitable equivalent, such asmetaly or" a hydrocarbon radical, or an amine res'i'dui In other'wor'ds, oneis'not limited to'the use of a polybasic carboxy' acid"; but" one might employ some suitable form in which one carboxy1ic'hy-- drogen atom' had alreadybeen replaced in a an". ner above described. For instance, one'm'ight'use sodium hydrogen phthalate, potassium" hydrogen phthalate, sodium hydrogen maleat'e'; potassium hydrogen maleate, octyl hydrogen" phthal'ate,

cetyl hydrogen maleate, ethyl hydrogen" primal ate,.or the like,.in place-or the'polybasit carb'oxy ticularly, an aliphatic alcohol, such as ethyl,

methyl, pro-pyl, butyl, or octyl alcohol; or one may eliminate the acidic hydrogen carboxyl if present by an amine, so as to form-a substituted ammonium salt; or if the amine is hydroxylated, as in For instance, diphthalated castor oil couldbe reacted with the Polybasic acidsnaving Ih'o'i 3 nitan, ,pentaerythritol, diglycerol, polyglycerol, diglycerol, diglycols, etc. Similarly,

ester in which the amine supplies the alkyl radical. Howevenwhere only on mole of a dibasic acid is employed for each mole'of higher molal carboxy acid, then both carboxyl radicals are involved in the reactions, without a residual carboxyl hydrogen atom being present.

In the preferred type of material, we employ a compound, in which, as has been previously indicated, a carboxyl group of the polybasic carboxy acid has been caused to unit With a hydroxylated detergent-forming acid body. As has been previously noted, thedetergent acids include fatty acids, particularlythe higher fatty acids, resin acids, petroleum acids, such as naturally-occurringpetroleum acids, and also petroleum acids obtained by the oxidation of parafiin hydrocarbons or the like. For the sake of brevity, reference will be made to phthalic anhydride. mole of phthalic anhydride may be esterified with a mole of ricinoleicacid, diricinoleic acid, polyricinoleic acid, chlororicinoleic acid, or the like;

Simi1arly,=one might employ an ester, such as ethyl ricinoleate,propyl ricinoleate, butyl ricinoleate, octyl ricin'oleate, benzyl ricinoleate, cyclohexyl' ricinoleate etca Another procedure would be to employ one or two moles of the phthalic anhydride and the 1 ester of a dih'ydric alcohol, such as ethylene glycol diricinolein, propylene glycol diricinolein, etc.

Similar derivatives --may be obtained from hyacids of the kind described in U. S. Patent No.

1,835,203, dated December 2, 1931, to -Br-uson.

Similarly,"one may employ the esters of glycerine,

, suchas triricinolein, trihydroxystearin," etc.

Instead of depending upon the hydroxyl group as being 'part of the acyl radical, one may, as previously suggested, employ compounds in which the hydroxyl radical is part of the polyhydric al- 3 cohol'residuer Thus, one might employ monostearin, mono olein, mononaphthenin, monoabietin, or similar compounds obtained from oxidized petroleumacids. One can also employ the type of materials in which there are two acyl groups attached to the polyhydric alcohol resionemay obtain materials of the kind in which there is at least one hydroxyl radical present as part of the acyl group, and at least, one hydroxyl radical present as part of the polyhydric alcohol residue, as, for example, monoricinolein, diricinolein, monohydroxystearin,'dihydroxystearin, the ricinolein mono-ester of ethylene glycol, or

similar glycols, etc.

The following are examples of the new compoour present invention, and which is adapted to be I used as a demulsifier in practising our process for I resolving petroleum emulsions:

Composition of matter, Example 1 An amine of the following type:

' the case of triethanolamine, one may form an One droxystearic' acid or polyhydroxylated stearic I triglycerol,

sition of matter that constitutes one feature of previously described is acylatedwith a molar pro-- portion of triricinolein monophthalate. I The product so obtained is entirely of the amide type,

Composition of matter, Example 2' The same procedure is followed astin the preceding example, except that an amine of the following'type is employed.

The material so obtained is largely the ester type, although there is present some of the amide type, and also some of the amide-ester type.

Composition of matter, Example 3 04m GHQ-CHEN om'onron.

(inborn-on om-oHFN CiHn' is 'employedfollowing the sameprocedure. as in Composition of matter, Example 1. The acylated product so obtained is entirely'of theester type.

Composition of matter, Example 4 An amine of the following typei NHCH2CHCH3 CH2 H Jan-0H Hz 011' iiH-oHrcn-om is employed, and one employs the same procedure as in Composition of matter, Example 1.

Composition of matter Example 5 The same procedure is employed-as in Composition of matter, Example 1, except that one employs either one of the following two amines or a mixture thereof: N-(2--hydroxy-3-aminopropyl)- 2-hydroxy propylene diamine-1,3; N,N-di(2-hydroxy-B-amino propyl) -2-'-hydroxy propylene diamine-1,3.

Composition o1" matter, Example 6 The same procedure is employed as in the preceding 7 examples, except that triricinolein diphthalate is employed.

Composition of matter, Example 9 The sameprocedure is followed as in the previous examples, except that mono.-olein monophthalate. is employed in place of triricinolein -monophthalate.- 1;,

l,3-diamino-2-propanol is acylated with triricmonophthalate.

ammo

Composition of matter, Example 'j'rnesame procedure is'iollowe'd as incompesition of niattr,'Examp1e 8, preceding, except tii at"mono-o1em diphthalate 'issubstitute'd 'fo'r triricinolein diphthalate.

Composition of matter, Example 11 Monoabietin monophthalate,- m'onoabietin diph-thalate, mononaphthenin monophthalate, and mononaphthem'n diphtha-late are substituted'in the-previous examplesthe monophthalated product replacing triricinolein monophthalatefand the :diphthalated products replacing triricinolein the fact that the diamines of the type described invariably contain at least one' reactive hydrogen atomjand "may contain 'more than one, "and in fact, 'usually' do contain more than one.

*Reabtive' hydrogenatoms, of course, refer-to such liyd'rogen-atoms, directly linkedto "nitrogen -br oxygen; i e., to hydroxyl hydrogenatomxor amino hydrogen atoms. The acyl group derived from-a polybasic carboxy acid' may beintroduced in "ei'ther position,- i'." e.,'- as a substituent for eith'er orbothty'p'es of reactive hydrogenatonis. When such group enters an amino hydrogen atom, *"it forms an amide. When it entersahyd'roxy'hydrogen atom position, it forms an ester. vigorous conditions of amidification one might obtain secondary amides. Onecan readily obtain the types in which there is both the amide 'link'agaand the" ester linkage. If desiredjon'e may have present an acyl group derived 'froma 'lo'wermole'cular weight acid, i. e.,'one havingfi "carbonatoms or less; for'instance,aceticfacid, 'propi'onic a'cid, "butyric acid, "or the like. The presence of such' acyl 'radical'is not intendedto fi'epresent' anything more than the equivalent-of "the'pr'esence of an alkylradi'cal.

"In general, all theacylation reactions of the kind described take place readily by reactions'in- 'volvin'g the selected materials in such a manner that any"water which'is formed is eliminated. Acylation can be accompanied by the elimination 'offsome other'eompound, such as NI-Is or HCl. Usually/this means'employment of a temperature above 120 C. and below the point'of 'decomposition. Generally, a temperature of 140-180C.'is f'mostsuitable. A dry, inert gas-may be passed through the mass during reaction to hasten acylation. It is understood, of course, that such acylation reactions 'do'not include salt formation. Inotherwords, ifthe intermediate raw-material "is" of the b'asic type, itcan form a salt with an acid such-as citric acid or phthalic "acid. On "heating such salt acylation products are obtained.

itation as ito': the I nature; or any ;carboxyl a'groups thatlrmayremain, 1 i. :e., without limitation :as :to being in Qthe acidic state or :neutralized .state.

This'may be illustrated in; the'rfollowing manner:

Under "Since at times there is some confusion as to "the --useof 'thewo'rd acyl or the like in con- "nection'with polybasic acids, insofar that there or more carboxy *hydroxyl groups, without l'im- If a polybasic acid .beiindicatedbyLthe followingi'formula: 1

in whichD represents a 'polybasic-acid'residue, m and n represent small 'wholenumbers, including zerogand' usually not-=over"three, --with the I proviso that m plus n must I be at least 2,- and Z represents any metal; ammonium radicalysubsti- 'tuted ammonium radical, or monovalent' organic radical '-'=which replaces a carboxylic hydrogen, "then examples ofacyl "radicals-derived iromsuch =pol-ybasic -'-carbox-y "acids include the following types:

coo-H cio oz D/ D/ co oo. ooon c-ooz, n ooon --DCO0Z co "co coon 00oz n co .o-co

00 v 0002 p 00 i -coon 'rhe w'ord' phthalyl will be given'l thencorre spending breadth of definition.

A .Insuch instances where the .amine containsat Tlea'sttwo hydroxyl radicals, or at least two amino hydrogen atoms, or at least ,one hydroxyl radical and at least one amino hydrogen atom, then one is dealing with a polyfunctionalor bifunctional compound; and thus reactions"involvingisuch ty es of Compounds with a polybasic acid .orldi- 'basic acid; 'suoh as phtha'lic anhydride, willproduce a sub-resinous or semi-resinous type .ofma- "terial. TCompare analogous reactions involving glycerol or glycol or monoethanolamine with .dibasic or polybasic acids. However, .diphthalated "triricin'olein, as any similar polycarboxy derivative will actinthe'same manner as phthalic anhydride. Our preferred reagent is derived from an amine which is polyfunctional and ismost desirably of the fsub-resinoustype, although itmaybe a monomer,

dimer, 'or'trimer. In other words, it is preferably 'a' compoundor admixture of compounds which still represents a liquid or plastic or fusible. mass at a' temperature in which the 'final-reactiomis -completed andis soluble'inone or more solvents "which-may be hydrophobe or hydrophile in nature, including solutions'of such acids as acetic acid, hydrochloric acid, etc. Polymers may rep- Tesentw'epeated monomers with elimination of *w'at'eror the like. I

"Certain; obviousfun'ctional "equivalents 'suggestthemselves and neednotbe described'in detail. For instance, a halogenated, ricinoleic acid body might'be employed just as advantageously 'asan -ordinary ricinoleic acid body. No advan- "tagewould'beobtained by the use of more expensive raw material. Similarly, chlorinated "-ph'thali'c anhydride'or'acid' might be used in place of the less-expensive raw'material.

It is to be noted that the expression alkyloxyalkyl is used in the hereto appended claims to indicate a radical in which the carbon atom .chainis interrupted at least once by oxygen and might be interrupted more than once, for instance, if derived from a compound obtained by the etherification of two moles of diethylene glycol.

In the hereto appended claims, the expression alkylol is not intended to be limited to monohydroxy alkyl radicals, but is intended to include polyhydroxylated .alkyl radicals.

It is to be noted that some of the compounds described are basic in character, due to the presence of an unacylated basic amino nitrogen atom, or due to the presence of an esterified group of the kind described. In such instances the compound may be employed as such, or may be employed in basic form (i. e., after combination with water), or may be employed in salt form by reaction with an acid, such as acetic acid, lactic acid, hydrochloric acid, or any other suitable acid.

Summarizing, then, what has been said, it will be appreciated that the present composition of matter may be characterized as acylated derivatives of a polyamine of the kind which can be characterized by the following formulas:

in which a: is a small whole number including 0, but in any event less than 10, and preferably 1 to 4; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type and D is hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RC0.0X',

RC0.0X", and RC0.0X"; in which RC is an acyl radical derived from a lower molecular weight carboxy acid having 6 carbon atoms or less; OX represents a divalent radical obtained at least hypothetically by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived at least hypothetically by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX represents'a divalent radical derived at least hypothetically by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived at least hypothetically by removal of a hydrogen atom from a hydroxyalkylamino radical.

As has been previously stated, the expression alkyl is intended at all times, particularly in the claims, to include products of the kind derived from ethyl chloracetate or the like; and the expression alkyloxyalkyl is intended similarly to include products in which the carbon atom chain is interrupted more than once by oxygen. This last statement is intended particularly to apply in respect to the hereto attached claims.

In the hereto appended claims, reference to a high molecular weight carboxy acid residue; a detergent-forming acid residue; a fatty acid residue, or a ricinoleic acid residue are inthe esters, such as the dehydroxylation of triricinolein, monostearin, distearin, mononaphthenin, dinaphthenin, mon'oabietin, diabietin, and'similar esters derived'from the glycols and characterized by the presence of an alcoholic hydroxyl as part of the polyhydric alcohol radical. 7

It is to be noted that some of the compounds described are basic in character, due to the presence of an unacylated basic amino nitrogen atom, or due to the presence of an esterified group of the kind described. In such instances the compound may be employed as such, or may be employed in basic form (i. e., after combination with water), or may be employed in salt form by reaction with an acid such as acetic acid, lactic acid, hydrochloric acid, or any other suitable acid.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is: g

1. A sub-resinous acylation derivative of a .polyamine of the following formula:

D N.T.(N.T)zND in which :n is a small numeral varying from 0 to 5; T is an oxyhydrocarbon radical selected from the class consisting of ketone, ether and alcohol radicals; and D is a member of the class. consisting of hydrogen atoms and alkyl, alkylol, hydroxyalkyl, oxyalkyl, and hydroxyalkylamino radicals,'the acyl group substituted for a reactive hydrogen atom of said polyamine being the acyl radical of an acidic fractional ester residue, which fractional ester in turn is characterized by the presence of:

(a) At least one detergent-forming monocarboxy acid radical; and (b) At least one'polybasic carboxy acid radical;

and said acylation derivative being additionally characterized bythe fact that there is at least one polybasic carboxy acid radical acting as a linking radicalbetween the amine residue and a detergent-forming monocarboxy acid residue; said detergent-forming monocarboxy acid residue havingat least 9 carbon atoms and not more than 32 carbon atoms, and said polybasic carboxy acid radical having notover Bcarbon atoms.

2. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is that of a higher fatty acid.

3. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is that of a higher unsaturated fatty acid.

4. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is that of a higher unsaturated fatty acid having 18 carbon atoms.

5. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is that of a higher unsaturated fatty acid having 18 carbon atoms and the polycarboxy acid radical is a dicarboxy acid radical.

6. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is a ricinoleyl radical and the polybasic carbox acid radical is a dicarboxy acid radical.

7. The acylation derivative described in claim 1, wherein the detergent-forming monocarboxy acid radical is a ricinoleyl radical and. the poly- 1 basic carboxy acid radical is a phthalic acid rad- 9. The acylation derivative described in claim ical. v 1, wherein the detergent-forming monocarboxy 8. The acylation derivative described in claim acid radical is a ricinoleyl radical and the poly- 1, wherein the detergent-forming monocarboxy basic carboxy acid radical is an-adipic acid radacidradical is a ricinoleyl radical and the poly- 5 ical. I basic carboxy acid radical is-a maleic acid rad- MELVIN DE GROOTE. ical. BERNHARD KEISER. 

